Phase formation in porous liquid phase sintered silicon carbide: Part I:: Interaction between Al2O3 and SiC

The structure and phase formation of porous liquid phase sintered silicon carbide (porous LPS-SiC), containing yttria and alumina additives have been studied. The present paper is focused on the system Al–Si–C–O, which is part of the system describing the interactions with sintering additives.The influence of different sintering atmospheres, namely argon and Ar/CO, and different temperatures on structure and composition was investigated by XRD and SEM. Additionally, reaction products were calculated from thermodynamic data and correlated with experimentally determined reaction products. Alumina and SiC reacted at 1950 °C in an argon atmosphere, forming a metal melt of aluminium and silicon. No reduction of Al₂O₃ was observed in a CO-containing argon sintering atmosphere.In the second and third parts of this paper the interactions between Y₂O₃–SiC and Y₂O₃–Al₂O₃–SiC are analysed [J. Eur. Ceram. Soc. (in press), parts II and III].     

Phase formation in porous liquid phase sintered silicon carbide: Part III: Interaction between Al2O3–Y2O3 and SiC

The structure and phase formation of porous liquid phase sintered silicon carbide (porous LPS-SiC), containing yttria and alumina additives have been studied. The present paper is focused on the system Y–Al–Si–C–O. The systems Al–Si–C–O and Y–Si–C–O have been studied in previous papers [J. Eur. Ceram. Soc. (in press) parts I and II].The reaction products of the interaction of Al₂O₃/Y₂O₃ with SiC and resulting microstructures were analysed by model experiments. The influences of different sintering atmospheres, namely argon and Ar/CO and different temperatures have been investigated. Thermodynamic calculations and sintering experiments reveal that silicides or carbides can be formed in addition to stable oxides. The main parameters controlling the formation of the different reaction products are the free carbon content, the oxygen activity and the temperature.Using CO containing atmospheres, the decomposition of the oxide additives can be effectively suppressed and stable porous LPS-SiC can be produced.     

Thermal conductivity of liquid-phase sintered silicon carbide ceramics: A review

Silicon carbide (SiC) exhibits excellent thermal conductivity. Recently, thermal conductivity that amounts to 261.5 W/m-K has been obtained in polycrystalline SiC ceramic liquid-phase sintered (LPS) with Y₂O₃-Sc₂O₃ additives at 2050 °C under a nitrogen atmosphere. From the additive used to the sintering atmosphere selected, many factors affect the thermal conductivity of the SiC. In this review, important factors that are known to determine the thermal conductivity of LPS-SiC (lattice oxygen/nitrogen content, porosity, grain size, grain boundary structure, phase transformation, and additive composition) have been evaluated. While reviewing the impact of each factor on thermal conductivity, hidden correlations among different factors are also discussed. Among the factors that are claimed to be important, we suggest a few factors that are more critical to thermal conductivity than others. Based on the most critical factors on the thermal conductivity of LPS-SiC, a complete engineers’ guide for high thermal conductivity LPS-SiC is proposed.     

Effects of sintering atmosphere on grain morphology of liquid-phase-sintered SiC with Al2O3 additions

The effects of sintering atmospheres of Ar and N₂ on grain morphology were investigated for pressureless liquid-phase-sintered (LPS) SiC with Al₂O₃ additions. When increasing the sintering temperature, the SiC grain size and its aspect ratio increased in both sintering atmospheres. With a 2 mass% Al₂O₃ addition, no distinct difference was observed between the grain morphology of SiC sintered in the Ar atmosphere and that sintered in the N₂ atmosphere. With a 15 mass% Al₂O₃ addition, sintering in a N₂ atmosphere led to retarded grain growth and this resulted in a fine homogeneous microstructure, whereas sintering in an Ar atmosphere enhanced the grain growth compared with that in 2 mass% Al₂O₃. The effects of atmosphere on the grain morphology depend on the amount of Al₂O₃ addition, and this also affects the grain growth process of solution-reprecipitation. The mechanical properties of the SiC are also considered.     

Low temperature pressureless sintering of α-SiC with Al2O3 and CeO2 as additives

The combination of Al₂O₃ and CeO₂ was testified as suitable sintering additive for liquid phase sintering of SiC ceramics, which has lower sintering temperature than that sintered with Al₂O₃ and Y₂O₃ as sintering aids. However, the mechanical properties including flexural strength, Vickers’ hardness and fracture toughness of this system were similar to those of the samples sintered with Al₂O₃ and Y₂O₃ as sintering aids. The good wettability of the eutectic liquid phase on SiC plate, the high solubility of SiC particles into the liquid phase and the penetration of the liquid phase along the SiC–SiC grain boundaries all confirmed the suitability of the combination of Al₂O₃ and CeO₂ as liquid phase sintering additive for SiC.     

Comparison of hydrothermal corrosion behavior of SiC with Al2O3 and Al2O3 + Y2O3 sintering additives

Fully dense SiC bulks with Al₂O₃ and Al₂O₃ + Y₂O₃ sintering additives were prepared by spark plasma sintering and the effect of sintering additives on the hydrothermal corrosion behavior of SiC bulks was investigated in the static autoclave at 400°C/10.3 MPa. The SiC specimen with Al₂O₃ sintering additive exhibited a higher weight loss and followed a linear law. However, the SiC specimen with Al₂O₃ + Y₂O₃ additive exhibited a lower weight loss and followed a parabolic law, indicating that the corrosion kinetic and mechanism were different for these two SiC bulks. Further examination revealed that, a deposited layer was formed on the surface of SiC specimen with Al₂O₃ + Y₂O₃ sintering additive after corrosion, which can effectively protect the SiC specimen from further corrosion, and thereby improved the corrosion resistance of the SiC specimen with Al₂O₃ + Y₂O₃ sintering additive.     

Al2O3–SiC composites prepared by infiltration of pre-sintered alumina with a poly(allyl)carbosilane

The Al₂O₃/SiC nanocomposites containing 3–8 vol.% SiC were prepared through infiltration and in situ thermal decomposition of a preceramic polymer SiC precursor (poly(allyl)carbosilane) in pre-sintered alumina matrix. The volume fraction of SiC, and the microstructure of composites were adjusted by concentration of the polymer solution, and by the conditions of pyrolysis and sintering. The specimens were densified by pressureless sintering at temperatures between 1550 and 1850 °C in flowing argon. The use of powder bed producing SiO, CO and other volatile species suppressed decomposition reactions in the composites and was vital for their successful densification. The experimental results are discussed against thermodynamic analysis of the system Al₂O₃/SiC/SiO₂ in an inert Ar atmosphere.     

Compositional identification of the intergranular phase in liquid phase sintered SiC

A model system consisting of coarse SiC (32–160 μm) as starting powder and Y₂O₃ and AlN as sintering additives was liquid phase sintered. Coarse-grained starting powder led to large intergranular phase regions which allowed an accurate determination of the chemical composition by wavelength-dispersive X-ray microanalysis (WDS). When N₂ was used as sintering atmosphere, a N-rich amorphous phase (about 44 at.% N) was identified by WDS to be the main triple-junction phase in the sintered SiC ceramics, while three further crystalline intergranular phases were AlN, Y₂SiN₄O₃ and an O-rich phase (Y₁₀Al₂Si₃O₁₈N₄). The overall O content was found to be reduced in comparison to the initial powder composition. The incorporation of N from the sintering atmosphere into the intergranular phase and a subsequent carbothermal reduction are believed to be responsible for the removal of O and the formation of the N-rich amorphous phase.     

Production of porous SiC by liquid phase sintering using graphite as sacrificial phase: Influence of SiO2 and graphite on the sintering mechanisms

Porous silicon carbide (SiC) is a promising ceramic for high-temperature applications due to its unique combination of properties. In the present work, a fabrication route for porous SiC is presented using graphite spherical powder as sacrificial phase to introduce porosity. By varying the initial amount of sacrificial phase, high-performance SiC materials with porosities in the range 30–50% were manufactured and characterized in terms of microstructure, density, thermal conductivity and flexural strength. The materials were fabricated by liquid phase sintering in presence of 2.5 wt.% Al₂O₃ and Y₂O₃ as sintering additives. The results indicate that the SiO₂ present in the starting SiC powders interacts with the sintering additives forming liquid phases that promote densification and weight loss. Besides, an Al-Si liquid phase is formed at higher sintering temperatures, whose contribution to densification is inhibited in presence of graphite due to the formation of Al-rich carbides.     

Effects of mechanically alloying Al2O3 and Y2O3 additives on the liquid phase sintering behavior and properties of SiC

In order to improve the sintering of SiC, mixtures of Al₂O₃ and Y₂O₃ powders are commonly included as sintering additives. The aim of this work was to use mechanically alloyed Al₂O₃–Y₂O₃ mixtures as sintering additives to promote liquid phase sintering of SiC using spark plasma sintering. The results showed that milling reduced the particle size of the powders and led to the formation of complex oxide phases (YAP, YAM, and YAG) at low temperatures. As the ball milling time increased, the mass loss of specimens sintered with mechanically alloyed Al₂O₃–Y₂O₃ mixtures decreased, and accordingly the relative density increased. However, the hardness and flexural strength of sintered SiC specimens first increased and then decreased. Because the specimens prepared with oxides milled for a long time contained too much YAG/YAP and accordingly too much liquid at sintering temperature. This negatively affected the mechanical properties of the SiC specimens because of the increased volume of the complex oxide phases, which have inferior mechanical properties to SiC, in the sintered specimens. When the ball milling time was 6 h, the hardness (24.02 GPa) and flexural strength (655.61 MPa) of the SiC specimens reached maximum values.     

Gelcasting and pressureless sintering of silicon carbide ceramics using Al2O3–Y2O3 as the sintering additives

In this paper, silicon carbide ceramics were prepared by aqueous gelcasting and pressureless sintering using Al₂O₃ and Y₂O₃ as the sintering additives. In order to develop well dispersed SiC slurries in the presence of sintering additives, the Al₂O₃ and Y₂O₃ powder was treated in the citric acid solution in advance. Zeta potential measurement showed that the isoelectric point (IEP) of Al₂O₃ and Y₂O₃ powder moved toward low pH region after treatment. Rheological measurement confirmed that the addition of as-treated powder showed very limited influence on the slurry properties as compared to that of untreated powder. SiC slurries with solid content of 54 vol% and enough fluidity can be developed. After gelcasting and pressureless sintering, SiC ceramics with nearly full density, fine grained and homogeneous microstructure can be obtained. Results showed that the surface treatment of Al₂O₃ and Y₂O₃ with citric acid is effective for the gelcasting process of SiC.     

Preparation and properties of porous SiC–Al2O3 ceramics using coal ash

In this paper, we first reported that porous SiC–Al₂O₃ ceramics were prepared from solid waste coal ash, activated carbon, and commercial SiC powder by a carbothermal reduction reaction (CRR) method under Ar atmosphere. The effects of addition amounts of SiC (0, 10, 15, and 20 wt%) on the postsintering properties of as-prepared porous SiC–Al₂O₃ ceramics, such as phase composition, microstructure, apparent porosity, bulk density, pore size distribution, compressive strength, thermal shock resistance, and thermal diffusivity have been investigated. It was found that the final products are β-SiC and α-Al₂O₃. Meanwhile, the SEM shows the pores distribute uniformly and the body gradually contacts closely in the porous SiC–Al₂O₃ ceramics. The properties of as-prepared porous SiC–Al₂O₃ ceramics were found to be remarkably improved by adding proper amounts of SiC (10, 15, and 20 wt%). However, further increasing the amount of SiC leads to a decrease in thermal shock resistance and mechanical properties. Porous SiC–Al₂O₃ ceramics doped with 10 wt% SiC and sintered at 1600°C for 5 hours with the median pore diameter of 4.24 μm, room-temperature compressive strength of 21.70 MPa, apparent porosity of 48%, and thermal diffusivity of 0.0194 cm²/s were successfully obtained.     

Effects of Y2O3 additives and powder purity on the densification and grain boundary composition of Al2O3/SiC nanocomposites

Sub-micron sized SiC additions can be used to increase the wear resistance and change the fracture mode of Al₂O₃. However, these additions also restrict sintering.Al₂O₃ and Al₂O₃–5%SiC ‘nanocomposites’ were prepared from alumina powders of high purity and of commercial-purity, with or without the addition of Y₂O₃. The effects of these compositional variables on sintering rate, final density and grain boundary composition were investigated. A direct comparison with Al₂O₃–SiO₂ composites was also made, as it has been proposed that SiC partially oxidises during processing of Al₂O₃–SiC nanocomposites.The addition of 5 vol.% SiC to Al₂O₃ hindered densification, as did addition of 0.15 wt.% Y₂O₃ or 0.1 wt.% SiO₂. In contrast, the addition of 0.15 wt.% Y₂O₃ to Al₂O₃–5% SiC nanocomposites improved densification.The composition of Al₂O₃–Al₂O₃ grain boundaries in these materials was studied using STEM and EDX microanalysis. The addition of SiC and SiO₂ caused segregation of Si, and Y₂O₃ addition caused segregation of Y. The segregation of each element was equivalent to <10% of a monolayer at the grain boundary. However, if SiC and Y₂O₃ were simultaneously added the segregation increased to 40% of a monolayer. The enhanced segregation was attributed to increased oxidation of SiC in the presence of Y₂O₃ allowing formation of a SiO₂–Al₂O₃–Y₂O₃ eutectic phase or a segregated layer which may explain the improvement in sintering rate when Y₂O₃ was added to nanocomposites.     

The effect of different sintering additives on the electrical and oxidation properties of Si3N4–MoSi2 composites

The fabrication and properties of electrically conductive Si₃N₄–MoSi₂ composites using two different sintering additive systems were investigated (i) Y₂O₃–Al₂O₃ and (ii) Lu₂O₃. It was found that the sintering atmosphere used (N₂ or Ar) had a critical influence on the final phase composition because MoSi₂ reacted with N₂ atmosphere during sintering resulting in the formation of Mo₅Si₃. The electrical conductivity of the composites exhibited typical percolation type behaviour and the percolation concentrations depended on the type of sintering additive and atmosphere used. Metallic-like conduction was the dominant conduction mechanism in the composites with MoSi₂ content over the percolation concentrations due to the formation of a three-dimensional percolation network of the conductive MoSi₂ phase. The effect of the sintering additives on the electrical and oxidation properties of the composites at elevated temperatures was investigated. Parabolic oxidation kinetics was observed in the composites with both types of additives. However, the Lu₂O₃-doped composites had superior oxidation resistance compared to the composites containing Y₂O₃–Al₂O₃. It is attributed to the higher eutectic temperature and crystallisation of the grain boundary phase and the oxidation layer in the Lu₂O₃-doped composites.     

Activation of Sintering of a Ceramics Based on SiC and Its Mechanical Properties

The technological conditions of fabrication, the phase composition, and the mechanical properties of sintered compositions in the SiC – Al₂O₃ – Y₂O₃ system are described. The processes occurring in their sintering are studied.     

Sintering of Al2O3-SiC composite from sol-gel method with MgO, TiO2 and Y2O3 addition

Al₂O₃-SiC composite ceramics were prepared by pressureless sintering with and without the addition of MgO, TiO₂ and Y₂O₃ as sintering aids. The effects of these compositional variables on final density and hardness were investigated. In the present article at first α-Al₂O₃ and β-SiC nano powders have been synthesized by sol-gel method separately by using AlCl₃, TEOS and saccharose as precursors. Pressureless sintering was carried out in nitrogen atmosphere at 1600 °C and 1630 °C. The addition of 5 vol.% SiC to Al₂O₃ hindered densification. In contrast, the addition of nano MgO and nano TiO₂ to Al₂O₃-5 vol.% SiC composites improved densification but Y₂O₃ did not have positive effect on sintering. Maximum density (97%) was achieved at 1630 °C. Vickers hardness was 17.7 GPa after sintering at 1630 °C. SEM revealed that the SiC particles were well distributed throughout the composite microstructures. The precursors and the resultant powders were characterized by XRD, STA and SEM.     

High temperature sintering of SiC with oxide additives: I. Analysis in the SiC–Al2O3 and SiC–Al2O3–Y2O3 systems

The vaporization behaviour of pure Al₂O₃, Y₂O₃ and SiC as well as SiC–Al₂O₃ and SiC–Al₂O₃/Y₂O₃ mixtures has been analysed by thermodynamic calculations in an open system. Pure Al₂O₃ and Y₂O₃ evaporate congruently in the 1200–2300 K temperature range. Pure SiC vaporizes in a non-congruent manner leading to graphite formation as by-product. A SiC–Al₂O₃ mixture evaporates congruently according to the main vaporization reaction, 2 SiC(s) + Al₂O₃(s) +Al₂O(g) ⇆ 2 SiO(g) + 2 CO(g) +4 Al(g), but the overall composition changes: for SiC rich samples, the mixture tends towards pure SiC in time, and for Al₂O₃ rich samples towards pure Al₂O₃. A SiC–Al₂O₃/Y₂O₃ mixture shows similar behaviour.     

In situ formation of mullite strengthened SiC porous ceramics via gelcasting with high strength and good alkali resistance

Mullite-bonded porous SiC ceramics sintered in air by gelcasting are still challenges due to the high porosity induced severe oxidation of SiC, which results in the formation of large amount of detrimental cristobalite phase. Here in this work, small amounts of Y₂O₃ and CaF₂ were added in SiC and Al(OH)₃ raw materials as sintering additives for the in situ growth of mullite reinforcement. This additive system promoted the reaction between oxidation-derived SiO₂ from SiC and Al₂O₃ decomposed from Al(OH)₃ to mullite phase. Almost no cristobalite phase was detected when sintered at 1450℃/2 h with CaF₂ addition of more than 2.0 wt%. Mullite whisker reinforcement was in situ formed due to the gas reaction mechanism caused by CaF₂ addition. Thus obtained porous SiC ceramics exhibited a flexural strength of 67.6 MPa at porosity of 41.3%, which maintained exceeding 36 MPa after 8 h corrosion in 10 wt% NaOH 80℃ solution, being the best performance up to now. This high performance of porous SiC was attributed to the additive induces proper phase control and in situ formation of whisker-like mullite reinforcement.     

Influence of Y2O3 addition on electrical properties of β-SiC ceramics sintered in nitrogen atmosphere

The influence of Y₂O₃ addition on electrical properties of β-SiC ceramics has been investigated. Polycrystalline SiC samples obtained by hot-pressing SiC–Y₂O₃ powder mixtures in nitrogen (N) atmosphere contain Y₂O₃ clusters segregated between SiC grains. Y₂O₃ forms a Y–Si-oxycarbonitride phase during sintering by reacting with SiO₂ and SiC and by dissolution of N from the atmosphere; this induces N doping into the SiC grains during the process of grain growth. The SiC samples exhibit an electrical resistivity of ～10^?3 Ω cm and a carrier density of ～10²⁰ cm^?3, which are ascribed to donor states derived from N impurities. The increase in defect density with increasing Y₂O₃ content is likely to be a main limiting factor of the electrical conductivity of SiC ceramics.     

Aqueous colloidal processing of SiC with Y3Al5O12 liquid-phase sintering additives

The aqueous colloidal processing of SiC with Y₃Al₅O₁₂ liquid-phase sintering additives was investigated for two different additive systems, one the mixture of Y₂O₃ and Al₂O₃ in a 3:5 molar ratio and the other directly Y₃Al₅O₁₂. The investigation involved the study of the colloidal stability of the different components, and the comparison of the rheological behaviour of concentrated suspensions of SiC, SiC + 3Y₂O₃:5Al₂O₃, and SiC + Y₃Al₅O₁₂ as a function of the sonication condition, dispersant content, and solid loading. This allowed appropriate conditions for the preparation of well-dispersed, single-phase, and multi-component concentrated suspensions of SiC to be identified. It was found that the multi-component suspensions have better rheological behaviour than the single-phase ones, and that in terms of rheology and slip casting the Y₃Al₅O₁₂ additives are more functional than the conventional 3Y₂O₃ + 5Al₂O₃ additives. It was also demonstrated that the Y₃Al₅O₁₂ additive is as effective as the 3Y₂O₃ + 5Al₂O₃ additive in densifying SiC via liquid-phase sintering, with there existing no differences either in the microstructure or in room-temperature mechanical properties (hardness, toughness, and fracture mode). Implications of interest for the wet-shaping of complex SiC parts are discussed.